JPH0693195A - Asymmetrical 1:2 metal complex of azo compound - Google Patents

Abstract

PURPOSE: To obtain an asymmetrical 1:2 metal complex of an azo compd. suitable for dyeing of an oxide layer on a surface of metal aluminum by adding a metal-free monoazo compd. to a 1:1 metal complex of a specified monoazo compd.

CONSTITUTION: A metal-free monoazo compd. of formula II (R₃ and R₄ are each H, a substd. or unsubstd. 1-4C alkyl or the like) is added to a 1:1 chromium or 1:1 cobalt complex or salt of a monoazo compd. of formula I (R₁ and R₂ are each H, a substd. or unsubstd. 1-4C alkyl or the like). Thereby, a mixture of an asymmetrical 1:2 metal complex of formula III (M is chromium or cobalt; M_k ⁺ is H or a non-chromophoric cation) and a mixture of complexes of formula III as well as salt thereof are obtained. The obtained complex of formula III is used pref. as a dye for dyeing a porous oxide layer comprising metal aluminum or aluminum alloy formed artificially on a surface of a support.

COPYRIGHT: (C)1994,JPO

Description

Detailed Description of the Invention

The present invention relates to asymmetrical 1: 2 metal complex azo compounds of chromium or cobalt containing sulphonic acid groups, their preparation and their use as anionic dyes.

More particularly, the present invention relates to the following formula I in free acid or salt form:

[Chemical 7](In the above formula, M is chromium or cobalt, and M_k ⁺
Is hydrogen or a non-color-forming cation, R₁And R₃Each of
Independently, hydrogen, C_1-4Alkyl or hydroxy, ami
C mono-substituted with no, sulfo or carboxy_1-4Archi
And R₂And R_FourEach independently, hydrogen, C_1-4A
Rutile; hydroxy, amino, sulfo or carboxy
C with a single substitution_1-4Alkyl; -COR_Five, -COOR₆Or-CON
HR ₇And R_FiveIs C_1-6Alkyl; hydroxy, halogen
N, C_1-4Set with alkoxy, sulfo or carboxy
Converted C_1-6Alkyl; Phenyl; Halogen, C_1-4Archi
Le, C_1-4Selected from alkoxy, sulfo and carboxy
Phenyl substituted with 1 or 2 groups;_1-4
Alkyl) or phenyl group is halogen, C_1-4Alkyl,
C_1-41 selected from alkoxy, sulfo and carboxy
Or phenyl substituted with two groups (C_1-4Alkyl)
R₆Is C_1-4Alkyl; hydroxy, halogen, C_1-4
C monosubstituted with alkoxy, sulfo or carboxy
_1-4Alkyl; Phenyl; Halogen, C_1-4Alkyl, C
_1-41 selected from alkoxy, sulfo and carboxy
Or phenyl substituted with two groups; phenyl (C_1-4Al
Kill); Phenyl is halogen, C_1-4Alkyl, C_1-4A
1 or 2 selected from lucoxy, sulfo and carboxy
Phenyl (C_1-4Alkyl); or shiku
Rohexyl, R₇Is hydrogen, C_1-4Alkyl; hydro
Mono-substituted with xy, amino, sulfo or carboxy
C_1-4Alkyl; Phenyl; Halogen, C_1-4Alkyl, C
_1-41 selected from alkoxy, sulfo and carboxy
Or phenyl substituted with two groups; or cyclohexyl
A) asymmetric 1: 2 metal complex and a complex of formula I
And a salt thereof.

In the present specification, an alkyl, an alkyl moiety of a phenyl-substituted alkyl group, or an alkyl group of an alkoxy group is linear or branched unless otherwise specified.

Halogen is preferably fluorine, chlorine or bromine, more preferably chlorine or bromine, especially chlorine.

In the hydroxy or amino substituted alkyl groups defined as R _{1 to} R ₄ and R ₇ , the substituents are preferably attached to carbon atoms which are not directly attached to the nitrogen atom. M is most preferably chromium.

The substituted alkyl groups defined as R _{1 to} R ₄ and R ₇ are preferably mono-substituted with hydroxy, amino or sulfo, more preferably hydroxy or amino.

The substituted alkyl group as R ₅ or R ₆ is preferably mono-substituted with hydroxy, chlorine, methoxy, sulfo or carboxy.

The substituted phenyl group or phenyl (C _1-4 alkyl) substituted on the phenyl ring preferably has 1 or 2 groups selected from chlorine, methyl, methoxy, sulfo and carboxy.

Preferably, one of the floating groups in ring A is in the ortho position and the other in the para position relative to --O--, ie the nitro and sulfo groups, are preferably in the meta position relative to each other.

In ring B, the chlorine and nitro positions are preferably 3-chloro / 5-nitro, 5-chloro / 3-.
Nitro and 5-chloro / 4-nitro, most preferably 3-chloro / 5-nitro.

R ₅ is preferably R _5a and R _5a is C _1-5.
Alkyl, phenyl or benzyl, more preferably R _5b , where R _5b is C _1-3 alkyl.

R ₆ is preferably R _6a , R _6a is methyl, ethyl, phenyl or benzyl, more preferably R _6b and R _6b is methyl or ethyl.

R ₇ is preferably R _7a , R _7a is hydrogen, methyl, ethyl, phenyl or cyclohexyl, in particular R ₇ is hydrogen.

[0014] R ₁ and R ₃ is preferably R _1a and R _3a, each of R _1a and R _3a are independently hydrogen, methyl, 2-hydroxyethyl or 2-aminoethyl.

[0015] R ₂ and R ₄ are preferably R _2a and R _4a, hydrogen each of R _2a and R _4a are independently methyl, -COR
_5a , -COOR _6b or -CONHR _7a , more preferably R ₂
And R ₄ are R _2b and R _4b , and each of R _2b and R _4b is independently hydrogen, —COR _5b or —CONH ₂ .

Most preferably, each of R ₁ -R ₄ is hydrogen, each amino group is preferably attached at the 3-position of each ring C and D, or the amino group of ring C is at the 2-position. , The amino group of ring D is in the 3-position and vice versa.

The preferred asymmetric 1: 2 chromium complex has the formula:
Ia

[Chemical 8](X in the above formula₁And X₂One is -NH₂And the others
-NH₂, -NHCH₃, -N (CH₃)₂, -NHCH₂C
H₂OH, -NHCH₂CH₂NH₂, -NHCOR _5a,
-NHCOOR_6b, Or -NHCONHR_7aAnd
R_5a, R_6a, And R_7aIs the same as the above rule, and M_{k '}
⁺Is a non-coloring cation).

More preferably, _one of X ₁ and X ₂ is -N
H ₂ and the other is —NH ₂ , —NHCOR _5a , or —NHCONH ₂ ,
R _5a has the same definition as above. Both X ₁ and X ₂ are -N
Particularly preferred is H ₂ .

The positions of the floating X ₁ and X ₂ are preferably as follows: X ₁ and X ₂ are preferably both in the 3-position, or _one of X ₁ and X ₂ is in the 2-position and the other is in the 3-position.

The present invention further comprises the following formula II

[Chemical 9] 1: 1 chromium or 1: 1 cobalt complex of the monoazo compound of the above formula (wherein R ₁ and R ₂ are the same as defined above) or a salt thereof, and the following formula III

[Chemical 10] A metal-free monoazo compound of formula I, wherein R ₃ and R ₄ are as defined above,
And a method for producing an asymmetric 1: 2 metal complex thereof.

The asymmetric 1: 2 chromium complex of formula I is prepared by reacting the metal-free compound of formula II and the metal-free compound of formula III, or salt thereof, described above, with a suitable amount of chromium (III). Manufactured in a process reaction. Chromium donating compounds are compounds of the formula in which at least 1 mol of chromium (III) salt is 2 mol
It is used in the amount used for the reaction with the metal-free compound of (II) and (III). This one-step reaction starts with 1: 1
It is carried out by maintaining the given reaction conditions such that a chromium complex is formed, which is not isolated and more metal-free azo compounds are added thereto.

Suitable metal-donating compounds are the conventionally used chromium (III) or cobalt (III) salts. The metallization (forming a 1: 1 or 1: 2 metal complex) is carried out by known methods.

For example, the conversion of metal-free azo compounds to 1: 1 chromium complexes is advantageously carried out at acidic pH (about 1.5 to
PH 3 and a temperature of 80-140 ° C or the boiling point of the reaction mixture, at atmospheric pressure or under pressure. The addition of the metal-free azo compound to the 1: 1 chromium complex is suitably carried out in a weak acid, neutral or weak alkaline medium (preferably from 6 to 6).
PH of 8) and the boiling point of the reaction mixture.

The reaction medium used is preferably water, if desired a water-miscible organic solvent such as formamide or ethylene glycol may be added.

Isolation of the 1: 2 metal complex of formula I is carried out by conventional methods, preferably by salting out and filtration.
A solution of the metal complex in an organic solvent is diluted with water. From this aqueous solution, the metal complex is precipitated by cooling and optionally adding a salt. The product is then isolated by filtration, then dried and, if desired, ground into a powder.

Depending on the reaction and isolation conditions, the 1: 2 metal complexes according to the invention may be in free acid form or in salt form with respect to the cations which neutralize the chromophoric complex anions or the cations which neutralize the sulphonic acid groups and the anionic groups present. can get.
The cation that neutralizes the complex anion is not a problem and can be any non-color forming cation common in the field of anionic metal complex dyes. Examples of suitable cations are alkali metal cations and unsubstituted or substituted ammonium ions such as lithium, sodium, potassium, ammonium, mono, di, tri and tetramethylammonium, triethylammonium, mono, di and triethanolammonium and mono, Di and triisopropanol ammonium. Preferred cations are alkali metal cations and ammonium, with potassium or sodium being most preferred.

Similarly, the sulfonic acid groups and other anionic groups are preferably in salt form. Suitable cations are those mentioned above which neutralize the complex anion. Usually 1: 2 of formula I
All cations present in the metal complex may be the same or different, preferably it is the same, with potassium or sodium being the most preferred cations.

The monoazo compounds of the formulas II and III used as starting materials are known and may be prepared by known methods from available starting materials.

The asymmetric 1: 2 metal complexes of the formula I are readily soluble in water and can be used in various materials, such as natural and synthetic polyamides,
For example, it is suitable for dyeing or printing wool, silk or nylon, polyurethane and leather. This complex is particularly suitable for dyeing or printing artificially formed oxide layers on the surface of metallic aluminum or aluminum alloys, ie layers formed preferably by chemical or anodizing processes in aqueous solution. The complexes of formula I are storage-stable prepared by dissolving the dyes in water, preferably with the addition of an organic solvent miscible with water and optionally with conventional auxiliaries such as solubilizers. It may be used in the form of an ionic liquid dye solution.

The oxide layer on aluminum dyed with the complex of the formula I shows high resistance to heat and good fastness and shows no bleeding.

Furthermore, the complexes of the formula I give fairly stable dye baths and have a high absorption rate. During the dyeing process, this complex is only slightly sensitive to aluminum ions.

The oxide layer formed by anodic oxidation means
Means a porous layer of aluminum oxide that adheres tightly to a base metal, such as that formed by electrochemical treatment of an aluminum surface in an electrolyte-containing water and a suitable acid with direct current by an aluminum workpiece forming the anode. To do.

In the field of surface treatment of aluminum,
The colored oxide layer formed by anodization is very important due to its excellent resistance to mechanical damage and corrosion. Conventional methods may be used to produce the pigmented oxide layer. Advantageously, the dyeing is carried out by adsorption dyeing, which is a method of impregnating anodized aluminum with an aqueous dye solution. This treatment is carried out at normal temperatures, ie from room temperature to the boiling point of the bath. 55
A temperature of ~ 65 ° C is particularly preferred. The pH is chosen so that the oxide layer is not attacked or only slightly attacked,
That is, the dyeing is carried out at a pH of 3-8, preferably 4.5-6. Adjustment and maintenance of pH is accomplished by the addition of conventional acids and bases such as sulfuric acid, acetic acid and sodium hydroxide. If desired, other additives used to improve the coloring process may be used, such as leveling agents, buffer systems and water-miscible organic solvents.

Dye concentrations and processing times vary widely depending on the strength of dye hue required, the thickness and structure of the oxide layer, and other dyeing conditions. The preferred concentration range is 0.01-
It is 10 g / l. The preferred treatment time is 1 to 30 minutes, 15
A processing time of ~ 20 minutes is particularly suitable.

Aluminum means not only pure aluminum but also aluminum alloys which behave like pure metals with respect to anodization, such as Al / Mg, Al / Si, Al / Mg /.
It means an alloy of Si, Al / Zn / Mg, Al / Cu / Mg and Al / Zn / Mg / Cu. Chromic acid, oxalic acid and sulfuric acid and mixtures of oxalic acid and sulfuric acid may be used as electrolytes for anodization. The direct current sulfuric acid method is the most preferable anodizing method. The dyeing may be performed at the same time when the oxide layer is formed as the anode.

The 1: 2 metal complex of the formula I is a chemically formed oxide layer on aluminum, a so-called conventional layer such as is formed by the action of an acid or alkali bath containing salts of chromic acid. Suitable for coloring.

After dyeing, the colored oxide layer is treated in the usual way. A particularly advantageous work-up method seals the oxide layer by treatment with boiling water or steam in the presence of a substance such as cobalt acetate or nickel, which optionally promotes sealing and at the same time prevents dye bleeding. That is.

The following examples further illustrate the present invention. In this example, parts and percentages are by weight and temperatures are in degrees Celsius unless otherwise noted.

Example 1 a) Preparation of 1: 1 chromium complex (1a) Diazotized 2-amino-4-nitrophenol-6-sulphonic acid and 2-amino-8-hydroxynaphthalene by conventional methods.
-6- Suspend 24.2 parts of azo dye (0.05 mol, calculated based on 100% active dye) obtained from the alkali coupling reaction with sulfonic acid in 300 parts of water. The pH is adjusted to 2.2 by adding a hydrochloric acid solution, then 2 parts of salicylic acid and 0.05 mol of chromium in the form of chromium (III) sulphate are added. The reaction mixture is heated to boiling, keeping the pH at 2.2 and boiling for a further 24 hours. After this, the reaction has ended and no starting material in the form of the metal-free azo compound is detected. The chromium complex 1a is isolated by filtering, washing with water and drying.

B) Preparation of asymmetric 1: 2 chromium complex (1b) 26.7 parts (0.05 mol, calculated on 100% activity basis) of 1: 1 chromium complex 1a are suspended in 600 parts of water. To this suspension was prepared by a conventional reaction by reacting disazotized 2-amino-6-chloro-4-nitrophenol with 2-amino-5-hydroxynaphthalene-7-sulfonic acid, 21.9 parts ( (Calculated based on 100% activity, 0.05 mol)
Add the azo dye. The pH of the reaction mixture was adjusted to 6-7 by adding sodium hydroxide and the solution was adjusted to 100
Heat to ℃. No starting material is detected after boiling for 3 hours. The resulting 1: 2 chromium complex 1b is salted out with sodium chloride, then filtered and dried. This is the formula

[Chemical 11] And dye anodized aluminum to black. The dyeing has good resistance to heat, good fastness to light and is resistant to bleed.

Example 2 The asymmetric 1: 2 chromium complex 1b of Example 1 is prepared in a one step reaction as follows. Diazotized 2-amino-4-nitrophenol-6-sulfonic acid and 2-amino-8- by known methods
12.1 parts obtained by reaction of hydroxynaphthalene-6-sulfonic acid (0.025 mol calculated based on 100% activity)
Metal-free dyes and diazotization by known methods
2-Amino-6-chloro-4-nitrophenol and 2-amino-5
-Hydroxynaphthalene-7-Sulfonic acid: 11 parts obtained by the reaction (calculated based on 100% activity, 0.025 mol)
Suspend the metal-free dye in 200 parts of water. The pH of this mixture is adjusted to 2.2 by adding hydrochloric acid. Then 6.2 parts (0.025 mol) of chromium (III) acetate are added and the suspension is stirred for 24 hours at boiling temperature. After adjusting the pH to 6.5 by adding sodium hydroxide, the reaction mixture is heated under boiling for a further 3 hours. After this time no starting material is detected. The chromium complex obtained by adding potassium chloride is precipitated, filtered and dried. The dyeing properties of the complex thus obtained are the same as those of the complex prepared by the method described in Example 1.

Examples 3 to 21 Other asymmetric 1: 2 chromium complexes shown in the table below are prepared by the method described in Examples 1 or 2 using the appropriate starting materials. These are represented by formula (A).

[Chemical 12]

The complexes of Examples 3 to 21 dye anodized aluminum in black. This dye obtained is a bleed,
It shows good properties in terms of fastness to light and resistance to heat.

[0044]

[Table 1]

The reaction and isolation conditions described in Examples 1 and 2 give the 1: 2 chromium complexes of Examples 3-21 similar to Example 1 (2) in the potassium salt form. This is converted by known methods into other salt forms or mixed salt forms containing one or more of the cations indicated above.

Example 22 35 parts of the dry dye of Example 1 are stirred at 60 ° C. in 65 parts of water. 100 parts of stable liquid uniform dyeing solution can be obtained. The dyeing liquor does not show precipitation even after long-term storage at 0 ° C or below, and when added to water, gives a clear solution within a very short time.

In the examples below, the application of the 1: 2 chromium complex is illustrated. Application Example A Pure aluminum degreased and deoxygenated workpieces are
A voltage of 15 to 16 volts and an aqueous solution containing 18 to 22 parts of sulfuric acid per 100 parts and 7.5 parts of aluminum sulfate 1.2 form 1.
30 at a temperature of 18 to 20 ° C with a current of 5 amps / dm ²
Anodize for minutes. An oxide layer with a thickness of about 12 μm is obtained.

After washing with water, the processed product was deionized water 10 the pH of which was adjusted to about 5.5 with acetic acid and sodium acetate.
Immerse for 15 minutes at 60 ° C. in a solution containing 5 parts of the chromium complex prepared according to Example 1 in 00 parts. The dyed work piece is washed with water and then sealed in deionized water at 98-100 ° C for 30 minutes. A pure black coloration is obtained and has good resistance to fading on exposure to heat and light.

When sealing is carried out in a solution containing 3 parts of nickel acetate in 1000 parts of water under the same conditions, a comparable quality of colouring is obtained.

Application Example B 10 parts of the dyestuff prepared in Example 1 are dissolved in 500 parts of water to give 400
Stir to a viscous solution consisting of 1 part water and 100 parts methyl cellosolve with a medium degree of polymerization and a degree of substitution of 1.5. The printing ink thus obtained is anodized with an aluminum alloy of Al / Mg / Si for 30 minutes in a solution of 100 parts chromic anhydride in 1000 parts water at a current density of 1.2 amps / dm ² and 53 ° C. The dried aluminum oxide sheet obtained in the above is applied by a screen printing method. The printed aluminum alloy sheet is soaked in boiling water for 10 minutes and then washed thoroughly with cold water. A black pattern is obtained on a light gray undercoat.

Similarly, the dye complexes of Examples 3 to 21 are used according to Application Examples A and B. In Application Example A, it is possible to use liquid dye liquors of the dyes of Examples 1-21.

The maximum absorption wavelength λ _max (nm) of the exemplified 1: 2 chromium complex is shown below. The values shown were measured in 0.1N sodium hydroxide solution.

Claims (8)

[Claims] 1. The following formula I in free acid or salt form:(In the above formula, M is chromium or cobalt, and_k ⁺Is hydrogen or a non-color-forming cation, R₁And R₃Each independently, hydrogen, C_1-4Alkyl or
Set with hydroxy, amino, sulfo or carboxy
Converted C_1-4Alkyl, R₂And R_FourEach independently, hydrogen, C_1-4Alkyl; hi
Mono-substituted with droxy, amino, sulfo or carboxy
Done C_1-4Alkyl; -COR_Five, -COOR₆Or-CONHR ₇And
R_FiveIs C_1-6Alkyl; hydroxy, halogen, C_1-4Al
C mono-substituted with coxy, sulfo or carboxy_1-6A
Rutile; phenyl; halogen, C_1-4Alkyl, C_1-4Al
1 or 2 selected from koxy, sulfo and carboxy
Phenyl substituted with a group of phenyl; phenyl (C_1-4Alkyl)
Is a phenyl group is halogen, C_1-4Alkyl, C_1-4Arcoki
1 or 2 groups selected from Si, sulfo and carboxy
Phenyl (C_1-4Alkyl) and R₆Is C_1-4Alkyl; hydroxy, halogen, C_1-4Al
C mono-substituted with coxy, sulfo or carboxy_1-4A
Rutile; phenyl; halogen, C_1-4Alkyl, C_1-4Al
1 or 2 selected from koxy, sulfo and carboxy
Phenyl substituted with a group of phenyl; phenyl (C_1-4Alkyl);
Phenyl is halogen, C_1-4Alkyl, C_1-4Arcoki
1 or 2 groups selected from Si, sulfo and carboxy
Phenyl (C_1-4Alkyl); or cyclohex
Sill, R₇Is hydrogen, C_1-4Alkyl; hydroxy, amino, sul
C monosubstituted with e or carboxy_1-4Alkyl; fe
Nyl; halogen, C_1-4Alkyl, C_1-4Alkoxy, sul
Substitute with 1 or 2 groups selected from e and carboxy
Phenyl; or cyclohexyl) asymmetric 1:
Mixtures of bimetallic complexes and complexes of formula I and salts thereof. 2. The asymmetric 1: 2 chromium complex according to claim 1. 3. The formula Ia below in free acid or salt form. (In the above formula, _one of X ₁ and X ₂ is —NH ₂ and the other is —N
_{H 2, -NHCH 3, -N (} CH 3) 2, -NHCH 2 CH 2 O
_{H, -NHCH 2 CH 2 NH 2} , -NHCOR 5a, -NH
COOR _6b or -NHCONHR _7a , R _5a is C _1-5 alkyl, phenyl or benzyl, R _6a is methyl or ethyl, R _7a is hydrogen, methyl, ethyl, phenyl or cyclohexyl. And M _{k ′} ⁺ is a non-color-forming cation).
The described complexes and mixtures thereof. 4. The complex according to claim 3, wherein X ₁ and X ₂ are both —NH ₂ . 5. A process for the preparation of an asymmetric 1: 2 metal complex of formula I according to claim 1, comprising the following formula II: A 1: 1 chromium or 1: 1 cobalt complex of the monoazo compound of the above formula (wherein R ₁ and R ₂ are the same as those defined in claim 1) or a salt thereof, and the following formula III A method comprising adding a metal-free monoazo compound of the above formula wherein R ₃ and R ₄ are the same as defined in claim 1. 6. A process for the preparation of an asymmetric 1: 2 chromium complex of formula I according to claim 1, comprising the following formula II: 1 mol of a metal-free compound or salt thereof and the following formula
III [Chemical 6] 1 mol of the metal-free compound or salt thereof (wherein R ₁ , R ₂ , R ₃ and R ₄ are the same as defined in claim 1) with at least 1 mol of chromium (III) salt A method comprising: 7. A method for dyeing or printing a support, which comprises coating the support with the complex according to claim 1. 8. An aluminum or aluminum alloy having an artificially formed oxide layer on the surface of a metal aluminum or aluminum alloy, wherein the support has an artificially formed porous oxide layer. ~ 4
Contacting with a solution of the complex according to any one of
The method of claim 7.